Fungicidal quaternary ammonium salts of dithiocarbamic acids



United States Tatent O FUNGICIDAL QUATERNARY ANIMONIUM SALTS OFDITHIOCARBAMIC ACIDS Mattheus H. C. 'M. Bakkeren and Jurrien J. Schuur,Groningen, Netherlands, assignors to N.V. Aagrunol Chemical Works,Groningen, Netherlands, a limitedliability company of the Netherlands NoDrawing. Filed May 20, 1959, Ser. No. 814,407

6 Claims. (Cl. 16722) This invention relates to fungicidal compositionsand processes which employ quaternary ammonium salts of substituteddithiocarbamic'acids and of ethylenebisdithiocarbamic acid.

Fungi infections of plants have in the past been minimized or preventedby application to the plants of sodium, zinc, iron and other such saltsof dithiocarbamic acids and similar salts of theethylenebisdithiocarbamic acid. These materials, however, will notcontrol a fungus infection which has become well established.

Mercurial fungicides have been used for the control of established fungiinfection but such mercurials are too toxic to be entirely satisfactory.

According to the present invention, the fungicidal compounds employedare, speaking generally, quaternary ammonium salts of dithiocarbamicacid. These com- A preferred scope of the invention may instead bestated by saying that according to the preferred form of the invention,the quaternary ammonium radical of the novel compound has a higher alkylgroup attached to the nitrogen atom, the remaining radicals attached tothe nitrogen atom being alkyl and/or aralkyl. Of course, when thequaternary ammonium radical is pyridinum,

three of the positions of the nitrogen atom constitute partmethyldithiocarbamic acid, diethyldithiocarbamic acid and pounds may beapplied to the objects or articles to be R is an aliphatic hydrocarbongroup of 10 to 18 carbons. R is hydrogen or an aliphatic hydrocarbongroup of less than 5 carbons.

carbons R is an aliphatic or aralkyl hydrocarbon group-of less than 13carbons.

R is methyl or ethyl.

agents,

ethylenebisdithiocarbamic acid.

The compounds as above described are extremely effective as fungicidesagainst plant pathogenic fungi and afford the valuable and unique effectof controlling such fungi even many hours after the incidence ofinfection. Often it is impossible to spray plants before the fungusinfection occurs and, particularly in rainy periods, it is impossible tospray soon enough after infection to control the disease. Thecompositions and methods of the present invention provide a way ofcontrolling such plant pathogenic fungi long after they would be pastcontrol by nonmercurial fungicides heretofore available.

The compositions and processes of the invention are especially valuablefor the control of fungi which infect trees such as fruit-bearing trees.Control of such fungi can be obtained up to three days after infection.

If desired. the composition which is used to treat the plants mayinclude, in addition to a compound or compounds of the presentinvention, other fungicides, insecti- "cides, and/or other agents forcontrolling noxious organisms.

The compounds employed according to the present invention are preferablyprepared by a double conversion of a soluble quaternary ammonium salt,such as chloride, with a soluble salt of a dithiocarbamic acid, such asa sodium salt.

R is an aliphatic hydrocarbon group ofless than 5 R is methyl or ethyl,or R R and R taken together with the nitrogen atom form the pyrindiumgroup.

While any of the dithiocarbamates above shown can be 55 employed, by farthe best results for the purposes of the present invention are obtainedusing those of Formula 1 in which Q is 3)z 'purifietl if desired.

Thus, a quaternary ammonium chloride is reacted with an equimolecularamount of an appropriate alkali metal dithiocarbamate in water toproduce a precipitate. This precipitate will contain impurities such asthe halide salt of the alkali metal and ordinarily the crude mixturethus obtained will be used as such in the composition and processes ofthe present invention. vAlternatively, the quaternary ammoniumdithiocarbamate can be further purified to separate it from the salt andany other impurities.

In like manner, two molecular equivalents of an appropriate quaternaryammonium halide can be reacted with one molecular equivalent of disodiumethylenebisdithiocarbamate, or another alkali metal ethylenebisdithio-.carbamate, in water to produce a precipitate. This can be used as suchor the dithiooarbamate portion can be Example 1 g.. of cetylpyridiniumchloride (0.25 mol) were dissolved in 600 ml. of water to which wereadded, while stirring, 3 6 g. sodium dimethyldithiocarbamate (0.252mol), dissolved in 180 ml. of water. g. of a palebrown colored product(cetylpyridinium dimethyldithioca'rbamate) were separated from thereaction mixture.

The fungicidal activity of this product was tested according to theslide germination method of evaluating fungicides (Phytopathology, 33,627-632) with regard to the fungi Clasterosporium carpophilum andFusarium morass? a solani. The LD-SO was found to 0.1 and 1.4 pzpnn'Example 2 Reaction of sodium dimethyldithiocarbamate with cetylpyridinium bromide to produce cetyl pyridinium dimethyldithiocarbamate.

Cetyl pyridinium bromide (38.4 grams, 0.1 mole) is dissolved in warmwater to give a 20% solution at 55 C. This solution is added over aZil-minute period, with stirring, to a solution of sodiumdimethydithiocarbamate (14.3 grams, 0.1 mole) in 130 ml. water. Aviscous brown solution forms which upon cooling to 5 C. forms a verythick slurry. The product is isolated by filtering, reslurrying in icewater, filtering and drying at room temperature. It is a brownish orangewaxy solid, melting at 55-61 C., and is sufficiently pure for fungicidalapplication. The small amounts of water and bromide ion contained inthis material may be removed by conventional means. For example, thewater may be removed by vacuum drying at elevated temperatures, and thebromide ion can be removed by recrystallization or chromatography overalumina, using chloroform as bath solvent and eluent. The purifiedproduct melts at LD-50 LID-50' Claszer- Fumrium ospnrium sola'nicarpophilnm Reaction product oi sodium dimethyldithio- I carbamate with:

3. stearyl trimethyl ammonium chloride.. 0. 1 2 4. dodecyltrimethylammonium bromide. u. 1 g. 5. tetradccyl trimethyl ammonium chloride 1 2G. stearyl dimethyl benzyl ammonium chloride 12. 5 7. rtizgtyl dimethylbenzyl ammonium chlo- 6 5 8 8. dodecyl dimethyl benzyl ammonium chloride0.6 8 Reaction product of disodium ethylenebisdithiocarbarr'ate with:

9. cetylpyridinium chloride 1.6 4 10. stearyl dimethyl benzyl ammoniumch1oride 10 14 11. cetyl dimcthyl benzyl ammonium chloride 6 '1 Reactionproduct of sodium meihyldithiocarbamate with:

12. cetylpyridinium chloride 0:5 4 13. tetradeeyl trimethyl ammoniumchloride 2 6 14. stearyl dimethyl benzy ammonium chloride 2' 10 15.cetyl dimethyl benzyl ammonium chloride 2 4 16. dodccyl dimethyl benzylammonium chloride 2 10 Reaction product oi sodium diethyldithiocarbamatewith:

17. cctyl pyridinium chloride 0.3 5 1S. tetradecyl trimcthyl ammoniumchloride 1.2 6 19. stearyl dimethyi benzyl ammonium chloride 0.2 2 20.cetyl dimethyl benzyl ammonium chloride 0.5 3 21. dodecyl dimethylbenzyl ammonium chloride 1 10 Further examples of quaternary ammoniumdithiocarbamates which can be used in compositions and process of theinvention are as follows:

Reaction product of sodium dimethyldithiocarbamate with:

22. Cetyl pyridinium chloride to make-cetyl pyridiniumdimethyldithiocarbamate 23. Cetyl pyridinium bromide to make cetylpyridinium dimethyldithiocarbamate 24. Tetradecyl pyridiniurn chlorideto make tetrae decyl pyrilinium dimethyldithiocarbamate 25. Cetyltrimethyi' ammonium bromide to make cetyl trimethyl ammoniumdimethyldithiocarbamate 26. Decyl isobutyl dimethyl ammonium bromide tomake decyl isobutyl dimethyl ammonium dimethyl dithiocarbamate 27.Tetradecyl triethyl ammonium chloride to make tetradecyl triethylammonium dimcthyldithiocarbamate 28. Stearyl pyridinium chloride to makestearyl pyridinium dimeihyldithiocarbamate 29. Dodecyl pyridiniumbromide to make dodecyl pyridinium dimethyldithiocarbamate 3'0. Stearyltriethyl' ammonium chloride to make stearyl triethyl ammoniumdimethyldithiocarbamate 31. Undecyl pyridinium chloride to make undecylpyridinium dimethyldithiocarbamate Reaction product of sodiumdiethyldithiocarbamate with:

32. Cetyl pyridinium bromide to make cetyl pyridiniumdiethyldithiocarbamate 33. Dodecyl pyridinium bromide to make dodecylpyridinium diethyldithiocarbamate 34. Stearyl benzyl dimethyl ammoniumchloride to make stearyl benzyl dimethyl ammonium diethyldithiocarbamate35. Stearyl pyridinium chloride to make stearyl pyridiniumdiethyldithiocarbamate 36. Cetyl triethyl ammonium chloride to makecetyl triethyl ammonium diethyldithiocarbamate 37.v Tetradecyl trimethylammonium chloride to make tetradecyl trimethyl. ammoniumdiethyldithiocarbamate 38. Decyl dimethyl benzyl ammonium bromide tomake decyl dimethyl-benzy'l ammonium. diethyldithiocarbamate 39. Dodecyltriethyl ammonium chloride tomake dodecyl triethyl ammoniumdiethyldithiocarbamate Reaction product of sodiumdi-n-butyldithiocarbamate with:

40. Cetyl pyridinium chloride to make cetyl pyridiniumdi-n-butyldithiocarbamate 4i. Tetradecyl trimethyl ammonium chloride tomake tetradecyl trimethyl ammonium di-n-butyldithiocarbamate 42. Cetyltrimethyl ammonium bromide to make cetyl trimethyl ammoniumdi-n-butyldithiocarbamate 43. Stearyl dimethyl benzyl ammonium chlorideto make stearyl dimethyl benzyl ammonium dimbutyldithiocarbarnate 44.Cetyl dimethyl benzyl ammonium chloride to make cetyl dimethyl benzylammonium di-n-butyldithiocarbamate 45. Dodecyl trimethyl ammoniumbromide to make dodecyl trimethyl ammonium di-n-butyldithiocar.- bamate46. Dodecyl dimethyl benzyl ammonium chloride to make dodecyl dimethylbenzyl ammonium di-nbutyldithiocarbamate 47. Tetradecyl' triethylammonium chloride to make tetradecyl triethyl ammoniumdi-n-butyldithiocarbamate 1 48. Stearyl trimethyl ammonium bromide tomake stearyl trimethyl ammonium di-n-butyldithiocarbamate 49. Decylisopropyl dimethyl ammonium chloride to make decyl isopropyl dimethylammonium di-nbutyldithiocarbamate Reaction product of disodiumethylenebisdithiocarbamate S0. Cetyl pyridinium'bromide to makecetylpyridinium e'thylenebisdithiocarbamate 51. Tetradecyl triethylammonium chloride to make tetradecyl triethyl ammoniumethylenebisdithiocarbamate 52. Tetradecyl pyridinium chloride to maketetradecyl pyridinium ethylenebisdithiocarbamate 53. Stearyl pyridiniumchloride to make stearyl pyridinium ethylenebisdithiocarbamate 54. Cetyltrimethyl ammonium chloride to make cetyl trimethyl ammoniumethylenebisdithiocarbamate 55. Stearyl n-butyl diethyl ammonium chlorideto make stearyl n-butyl diethyl ammonium ethylenebisdithiocarbamate 56.Dodecyl trimethyl ammonium bromide to make dodecyl trimethyl ammoniumethylenebisdithiocarbamate q 57. Stearyl trimethyl ammonium chloride tomake stearyl trimethyl ammonium ethylenebisdithiocarbamate 5 8. Decyltriethyl ammonium chloride to make decyl triethyl ammoniumethylenebisdithiocarbamate 59. Undecyl trimethyl ammonium chloride tomake undecyl trimethyl ammonium ethylenebisdithiooarbamate 60. Stearyltriethyl ammonium chloride to make stearyl triethyl ammoniumethylenebisdithiocarbamate 61. Stearyl benzyl diethyl ammonium chlorideto make stearyl benzyl diethyl ammonium ethylenebisdithiocarbamateReaction product of sodium di-n-propyldithiocarbamate with 62. Cetylpyridinium bromide to make cetyl pyridinium di-n-propyldithiocarbamate63. Stearyl trimethyl ammonium chloride to make stearyl trimethylammonium di-n-propyldithiocarbamate Reaction product of sodiumN-methyl-N-ethyldithiocar- Reaction product of sodiumN-methy-l-N-isopropyldithiocarbamate with:

bamate with:

64. Cetyl pyridinium chloride to make cetyl pyridiniumN-methyl-N-ethyldithiocarbamate 65. Dodecyl benzyl diethyl ammoniumchloride to make dodecyl benzyl diethyl ammonium N-methyl-N-ethylenedithiocarbamate Reaction product of sodiumN-methyl-N-(n-butyl)dithio- Reaction product of sodiumN-ethyl-N-(n-propyl)dithiocarbamate with:

Reaction product of sodium N-ethyl-N-isobutyldithiocarbamate with:

68. Dodecyl methyl diethyl ammonium chloride to make dodecyl methyldiethyl ammonium N- methyl-N- (n-butyl dithiocarb amate 69. Stearylpyridinium chloride to make stearyl pyridinium N-methyl-N-(n-butyl)dithiocarbamate 70. Stearyl decyl dimethyl ammonium chloride to makestearyl decyl dimethyl ammonium N-ethyl- N- (n-propyl dithiocarbamatecarbamate with:

71. Tetradecylpyridinium chloride to make tetradecyl pyridiniumN-ethyl-N-isobutyldithiocarbamate Reaction product of sodiumN-(n-propyl)-N-(n-butyl)- dithiocarbamate with:

72. Cetyl benzyl dimethyl ammonium chloride to make cetyl benzyldimethyl N-(n-propyl)-N-(nbutyl) dithiocarbamate 73. Cetyl pyridiniumbromide to make cetyl pyri- Reaction product of sodiumethyldithiocarbamate with: 74. Cetyl pyridinium bromide to make cetylpyridinium ethyldithiocarbamate 75. Cetyl dimethyl benzyl ammoniumchloride to make cetyl dimethyl benzyl ammonium ethyldithio carbamateReaction product of sodium n-propyldithiocarbamate with:

76. Tetradecyl trimethyl ammonium chloride to make tetradecyl trimcthylammonium n-propyldithiocarbamate 77. Decyl triethyl ammonium bromide tomake decyl triethyl ammonium n-propyldithiocarbamate Reaction product ofsodium n-butyldithiocarbamate with:

78. Cetyl pyridinium chloride to make cetyl pyridiniumn-butyldithiocarbamate 79. Dodecyl dimethyl benzyl ammonium chloride tomake dodecyl dimethyl benzyl ammonium n-butyldithiocarbamate Theappropriate quaternary ammonium halide was in each instance reacted withthe dithiocarbamate as set out in Examples 1 and 2 above. Thus, in eachinstance, equimolecular amounts of the reactants are dissolved in waterand reacted to form a precipitate.

Fungicidal compositions of the present invention containing at least oneof the quaternary ammonium products as above described can be preparedby admixing one or more of these products with pest control adjuvants ormodifiers to provide compositions in the form of waterdispersiblepowders, dusts, solutions, and emulsifiable solutions. While thequaternary ammonium dithiocarbamates employed in compositions of theinvention can be formulated in any conventional manner and used inprocesses of the invention for the control of fungi, it is muchpreferred that they be formulated in compositions which contain afree-flowing, inert powder. Still more preferred are such. mixtures inwhich one or more surfactants are present.

The free-flowing, inert powders can be any of the extenders commonlyemployed in the insecticide, herbicide and fungicide art for theapplication of such materials and may include natural clays such asattapulgite and kaolinite clays, diatomaceous earth, talcs, syntheticmineral fillers derived from silica and silicate such as synthetic finesilica and synthetic calcium or magnesium silicate, wood flour andwalnut shell flour.

' The amount of the extenders can vary widely and can range from about10 to 95% by weight of a fungicidal composition. Thus the amount ofdithiocarbamate will range from about 5 to ,The particle size can varyconsiderably but will ordinarily be somewhat under 50 microns in thefinished formulation. As a'matter of convenience, the compositions canbe prepared with a pulverulent extender or with an extender withparticles above the desired size and after admixture with the quaternaryammonium dithiocarbamate the entire composition can be suitably groundso that the particle size of the extender will be small enough to givefree-flowing compositions which can readily be applied. Particle sizewill usually run something under 50 microns in such finished products.

Compositions as described can, in addition to the finely dividedextender, contain a surfactant. The surfactant can be a dispersant, ade-foamer or an emulsifying agent which will assist dispersion of thecomposition in the water. The surfactants or surface-active agents caninclude such cationic and non-ionic surface-active agents as haveheretofore been generally employed in pest control compositions ofsimilar type. Suitable surface-active agents are set out, for example,in Searle US. Patent 2,426,417, Todd US. Patent 2,655,447, Jones US.Patent 2,412,510, or Lenher US. Patent 2,139,276. A detailed list ofsuch agents is set forth by J. W. McCutcheon in Soap and ChemicalSpecialties, December 1957, Januseats;

ary, February, March and April 1958. See also Mc- Cutcheon in ChemicalIndustries, November 1947, page 8011 et seq., entitled SyntheticDetergents; and Bulletin E-607 of the Bureau of Entomology and PlantQuarantine of the US. Dept. of Agriculture. In general, anionicsurface-active agents cannot be used.

Suitable surfactants for use in compositions of the present inventionare alkyl and alkyl aryl polyether alcohols, polyoxyethylene sorbitol orsorbitan fatty acid esters, polyethylene glycol fatty esters and fattyalkylol amide condensates.

In general, less than about by weight of the surface-active agent willbe used in compositions of the invention and ordinarily the amount ofsurface-active agent will be less than 1% by Weight. Usually, inaccordance with customary practices, the amount will range from about0.5 to 2% of a surface-active agent.

Particularly preferred surface-active agents include polyvinyl alcohol,methocels, gum arabic, long chain amine acetates, substituted oxazolinesand alkyl dimethylamine oxides.

The quaternary ammonium dithiocarbamates used in compositions of theinvention are very slightly water soluble and are cationic in nature,thus, to greater or lesser extents, various of the compounds abovedescribed act as wetting and dispersing agents. This action, however,will often be insufiicient and a suitable non-ionic or cationicdispersant should also be added.

While formulations containing free-flowing, finely divided extenders andwith or without an added wetting agent are much preferred compositionsof the invention, it Will be understood that the quaternary ammoniumcompounds can be used in processes of the invention by formulation andapplication in various conventional manners.

Thus, the compounds though only slightly soluble can be dissolved inwater at the point of use to obtain enough of the active material toobtain control of fungi.

The quaternary ammonium compounds to be used in the processes of theinvention can also be dissolved in appropriate non-phytotoxic organicsolvents. A concentrate thus formed can be mixed with water, using adispersing agent if one is necessary. This cetylpyridiniumdimethyldithiocarbamate can be dissolved to form a concentrated solutionin dimethylformamide and this can be mixed with an appropriate quantityof water to obtain the concentration of the dithiocarbamate desired.Other suitable solvents are lower molecular weight aromatichydrocarbons, usually benzene, toluene, xylene and alkylatednaphthalene, volatile, low molecular weight esters, and water immiscibleketones such as ethyl to amyl acetate and methylisobutyl ketone todibutyl ketone.

Emulsifiable oils can be prepared in the same fashion using an oil inwhich the dithiocarbamate is soluble, such as xylene. Such emulsifiableoils can contain other suitable solvents for the quaternary ammoniumdithiocarbamates as above. With such oils, suitable surfactants shouldbe used such as cationic or non-ionic agents known to the art asemulsifying agents as above described.

In the application of quarternary ammonium dithiocarbamates according tothe invention, fungicidal control is obtained by applying the activecompound at a dosage, or at a rate, from about 0.05 to 5 pounds peracre. The optimum amount in each instance is largely dependent upon theexact method of application, the state and condition of growth of plantsto be treated, the climatic conditions and other such well-understoodvariables.

pear scab, peach scab, cedar-apple rust, cherry leaf spot, .Broolrsspot, sooty blotch, bitter rot, black rot, black spot (of roses) andapple blotch.

. 8 Example 80 A fungicidal composition was prepared by mixing 20 partsby weight of cetylpyridinium dimethyldithiocarbamate with parts byweight of a filler (fullers earth) and 10 parts byweight of dispersingagent (refined sulfite lye powder). This composition is identified ascomposition A in Tests I and II below and is sprayed in the form of a.suspension containing 0.2% of composition A.

The above composition was compared with composition Z containing of zincdimethyldithiocarbamate in two tests for controlling Venturia inaequalis(apple scab) on the James Grieve variety. The results were as follows:

Test 1.The trees were sprayed 24 hours after infection of the leaf.After spraying 20 days elapsed before the percentage of leaf surfaceaffected by scab was determined.

Test II.-The trees were sprayed as in Test I but this time 48 hoursafter infection of the leaf. After spraying 19 days elapsed before thepercentage of leaf surface affected by scab was determined.

Average percent of leaf surface affected by scab Treatment of tree 1Composition Z, 0.1%. Composition A, 0.2%. 0.2

Example 81 Percent Cetyl pyridinium dimethyldithiocarbamate 20Attapulgite clay 80 The above composition is prepared by blending thecomponents together and passing through a micropulven'zer untilsubstantially all agglomerates are broken down to 50 microns or smaller.

This formulation is applied at the rate of 2 pounds per gallons of waterto an apple orchard 48 hours after a scab infection period. Excellentcurative action on the scab infection is obtained and the trees areprotected from re-infection by the disease.

Example 82 Percent Cetyl trimethylammonium dirnethyldithiocarbamate 50Low viscosity polyvinyl alcohol 1 Synthetic fine silica 49 The abovewettable powder is prepared as in Example 81.

This formulation is applied at the rate of 1 /2 pounds per 100 gallonsin the first cover spray for control of apple scab and cedar-apple rustin an apple orchard. Good control of both diseases is obtained.

Example 83 Percent Cetyl pyridinium dimethyldithiocarbamate 20 A blendof long chain fatty amides 2 Xylene 78 The above emulsifiablecomposition is prepared by simple mixing of the mutually solublecomponents. When dispersed in water this compositions forms a cationicemulsion. i

This formulation is applied at the rate of 1 pint per 100 gallons toagrove of Bartlett pears as a preventive treatment for control of pearscab. Sprayed trees are protected from the disease while unsprayed treesare severely infected with scab.

Example 84 Percent Dodecyl tn'methylammonium dimethyldithiocarbamate 25Attapulgite clay 75 Example 85 Percent Tetradecyl trimethylammoniumdimethyldithiocarbamate Diatomaceous silica The above wettable powder isprepared in the same manner as Example 81.

This formulation is applied at the rate of 2 pounds per 100 gallons to apear orchard 48 hours after a scab infection period. Developing scablesions on the leaves are eradicated and the trees protected from earlyreinfection by scab and also from sooty blotch disease.

Example 86 Percent Cetyl dimethyl benzylammonium dimethyldithiocarbamate10 Attapulgite clay 40 Pyrophyllite 50 Example 87 Percent Tetradecyltrimethylammonium diethyldithiocarbamate 50 Synthetic fine silica 50 Theabove wettable powder is prepared in the same manner as Example 81.

This composition is included at a rate of /1 pounds per 100 gallons inthe shnck-fall spray in a cherry orchard for control of cherry leafspot. Excellent control of the disease is obtained on the treated trees.

Example 88 Percent Stearyl dimethyl benzylammoniumdiethyldithiocarbamate 50 Synthetic fine calcium silicate (neutral) 50The above wettable powder is prepared in the same manner as Example 81.

This composition is applied at the rate of 1 pound per 100 gallons to aninterplanted apple and peach orchard for the control of apple scab,peach scab, sooty blotch, and frog-eye leaf spot. Good control of bothapple and peach diseases results.

Example 89 Percent Cetyl pyridinium ethylenebisdithiocarbamate 20 Mixedlong chain fatty amides 2 Xylene 78 The 'above emulsifiable oil isprepared in the same manner as Example 83.

This composition is applied to a planting of crab apple tree forprotection from attack by apple scab. A rate of 1 pint per acre is used,and good protection is afforded from the fungus disease.

Example 90 Percent Cetyl dimethyl benzylammoniumethylenebisdithiocarbamate l0 Attapulgite clay 30 Micaceous talc 60 Theabove dust is prepared by first blending and grinding the activecomponent with the minor diluent until substantially all agglomeratesare reduced to below 50 microns, then blending this mix with the majordiluent.

A row of grapes is dusted just prior to bloom with this composition atthe rate of 10 pounds per acre for protection against black rot.Repetition of the treatment immediately after bloom and at two weeksafter bloom gives good control of the disease.

Example 91 Percent Cetyl trimethylammonium ethylenebisdithiocarbamate 25Attapulgite clay The above wettable powder is prepared in the samemanner as Example 81.

An apple orchard is sprayed 24 hours after a scab infection period withthis composition at a rate of 1 pound per 100 gallons. Scab lesionswhich have begun are eradicated from the leaves and the trees are thusprotected from this disease.

The compounds above numbered 1 to 79 can be formulated in each of theways shown. Thus in each of the Examples to 91 above, the quaternaryammonium dithiocarbamate there named can be replaced with an equalweight of the quaternary ammonium dithiocarbamate of Examples 1 to 79and applied as shown.

This application is a continuation-in-part of copending applicationSerial No. 779,559, filed December 11, 1958, now abandoned.

The claims are:

1. A method for controlling plant pathogenic fungi comprising applyingto a plant a fungicidally elfective amount of:

R1 s R4I 1"i i 3Q R|/ Rs in which:

Q is selected from the group consisting of R is an alkyl hydrocarbongroup of 10 to 18 carbons R is selected from the group consisting ofhydrogen and an alkyl hydrocarbon group of less than 5 carbons,

R is an alkyl hydrocarbon group of less than 5 carbons,

R is selected from the group consisting of an alkyl and aralkylhydrocarbon group of less than 13 carbons, and, when R N and R takentogether comprise a pyridinium group, a merged constituent of such pyri'dinium group,

R is selected from the group consisting of methyl and ethyl,

. 1-1 V R, is' selected from the group consisting of methyl, ethyl, and,when R N, and R taken together comprise a pyridinium group, a mergedconstituent ofsuchpyridinum group.

2. A method for controlling plant pathogenic fungi comprising applyingto a plant a fungicidally' effective amount of cetyl pyridiniumdimethyldithiocarbamate.

3. A method for controlling plant pathogenic fungi comprising applyingto a plant a fungicidally effective amountof cetyl pyridiniumethylenebisdithiocarbamate.

4. A methodfor-controlling plant pathogenic fungi comprising applying toa planta fungicidally efl'ective amount of cetyl pyridjninmmethyldithiocarbamate.

5-. A method for controlling plant pathogenic fungi" comprising applyingto a plant a fungicidally effective amountof cetyl pyridiniumdiethylidthiocarbamate;

6. A fungicidal formulation containing 5 to 90% ofthe compound describedin claim 1, the balance consisting essentially of a finely divided,free-flowing, inert extender and: containing additionally asurface-active.

UNITED STATES PATENTS 2,457,674 Heuberger t. -j.. Dec. 28, 1948.

Baird Sept. 27, 1938

1. A METHOD FOR CONTROLLING PLANT PATHOGENIC FUNGI COMPRISING APPLYINGTO A PLANT A FUNGICIDALLY EFFECTIVE AMOUNT OF: